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APPLICATIONS OF ELECTRON MICROSCOPY IN MATERIALS

AND METALLURGICAL ENGINEERING

A TERM PAPER

PRESENTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS


FOR THE POSTGRADUATE COURSE
MME 604
[ELECTON OPTICS AND MICROSCOPY]

BY

MARK, UDOCHUKWU
20044449298

SUBMITTED TO

ENGR. PROF. O. O. ONYEMAOBI [EXAMINER]

DEPARTMENT OF MATERIALS AND METALLURGICAL ENGNEERING


FEDERAL UNIVERSITY OF TECHNOLOGY, OWERRI

AUGUST 2005

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PREFACE

The electron microscope is an indispensable modern analytical and research

tool. Microscopy is employed in all branches of science to identify materials,

characterize unknown substances or study the properties of known materials.

This term paper surveys the applications of electron microscopy in the field

of materials and metallurgical engineering.

I hereby acknowledge my lecturer on Electron Optics and Microscopy

(MME 604), Engr. Prof. O. O. Onyemaobi. He has been sharpening my

research and writing skills since my undergraduate days. This is the third

term paper I will be submitting to him.

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TABLE OF CONTENTS

Title Page i

Preface ii

Table of Contents iii-v

CHAPTER ONE 1-12

1.0 Introduction 1

1.1 Materials and Metallurgical Engineering 1

1.2 Microscopes and Microscopy 3

1.2.1 Levels of Structure 4

1.2.2 Methods of Structural and Compositional Elucidation 6

1.2.3 Microscopy 8

CHAPTER TWO 13-24

2.0 Transmission Electron Microscopy 13

2.1 Interaction of Electrons with Solids 13

2.2 Transmission Electron Microscope (TEM) 14

2.3 TEM Modes and Applications 16

2.3.1 General 17

2.3.2 Surface Information & External Morphology 18

2.3.3 Contrast from an Imperfect Crystal 19

2.3.4 Precipitates and Second Phases 21

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2.3.5 Specialized Techniques of TEM 21

CHAPTER THREE 25-41

3.0 Scanning Electron Microscopy 25

3.1 Scanning Electron Microscope (SEM) 25

3.2 SEM Modes and Applications 27

3.2.1 The Reflective and Emissive Modes 28

3.2.2 Absorptive Mode 33

3.2.3 Conductive Mode 33

3.2.4 Luminescent Mode 35

3.2.5 X-Ray and Auger Modes 36

3.3 Exploiting the Versatility of SEM 40

CHAPTER FOUR 42-47

4.0 The STEM and Other Developments 42

4.1 Scanning Transmission Electron Microscope 42

4.2 Applications of the STEM 43

4.3 High Resolution STEM 44

4.4 The TEM at High Voltages 44

4.5 Analytical TEM 46

4.6 Energy Analyzing Microscopes 47

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CHAPTER FIVE 48-62

5.0 Special Techniques of Surface Microscopy and Analysis 48

5.1 Introduction 48

5.2 Acoustic and Thermal Wave Imaging 49

5.3 Field – Electron and Field – Ion Emission 51

5.3.1 Field – Electron Microscopy 52

5.3.2 Field-Ion Emission and Field-Ion Desorption

Microscopy and the Atom Probe 53

5.4 Photon - Induced Radiation 54

5.4.1 X-Ray Microscopy and Topography 55

5.4.2 Fluorescence Microscopy and Spectroscopy 56

5.5 Photo-Electron Emission 57

5.5.1 Photo-Electron Emission Microscopy 57

5.5.2 Photo-Electron Spectroscopy 58

5.6 Electron-Beam and Ion-Induced Radiation 58

5.7 Electron-Electron Interaction 60

5.8 Ion Spectroscopy 61

CHAPTER SIX 63-64

6.0 Conclusion 63

References 65-67

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CHAPTER ONE

2.0 INTRODUCTION

1.1 MATERIALS AND METALLURGICAL ENGINEERING

The title of this paper indicates an interest in the field of materials and

metallurgical engineering. It is therefore necessary to define these

disciplines as to give this treatise both direction and scope.

Metallurgy or metallurgical engineering is the science and technology of the

production, properties and uses of metals and their alloys. It is concerned

with every aspect of metals processing; their extraction from ores or

recycled components, their refining, shaping and manufacturing processes,

and the exploitation of their physical and mechanical properties for

application in every sector of industry8. Materials engineering is all about

metallurgical engineering except that it de-emphasizes metals and focuses on

non-metallic materials. It is therefore interested in the production and

properties of a wide range of materials, including electronic materials, glass

and ceramics, polymers and many other natural and man-made materials.

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The nucleation, growth and development of materials and metallurgical

engineering disciplines followed a unique trend. First, metallurgy was

recognized because of the extensive use of metals. With the diversification

of engineering materials beyond primary metals and their alloys, it became

necessary in the late 1960s to recognize as it were, the ‘metallurgy’ of non-

metallic materials. Hence, materials engineering was born in the early 1970s.

Finally, materials and metallurgical engineering fields have metamorphosed

into a composite discipline called Materials Science and Engineering. This

came in the 1990s as a result of the classification of engineering materials,

and the recognition of the fact that the same principles of science and

technology underlie their production, properties and uses. In this view,

metals are considered as a class of engineering materials, so that materials

science and engineering covers and includes the field of metallurgy.

This term paper therefore, may have been better titled, ‘Applications of

Electron Microscopy in Materials Science and Engineering’. Materials

science and engineering includes both the basic knowledge (the science) and

the applied knowledge (the engineering) of materials. The term engineering

materials is used to refer specifically to solid materials used to produce

technical products. Broadly speaking, they include metals and alloys,

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ceramics and glass, polymers, and composites. By this definition, liquids and

gases are ruled out. Again, solid-state physics and chemistry are implied in

the term materials science, so that the biological sciences are not

considered.15, 16, and 18

In conclusion, this term paper shall survey the applications of electron

microscopy in the physical sciences; specifically in physical metallurgy,

extractive metallurgy and mineral processing, polymer & textile technology,

corrosion studies, mechanical metallurgy, microelectronics and

nanotechnology, etc.

1.2 MICROSCOPES AND MICROSCOPY

Present-day materials science depends heavily on understanding how the

properties of a material relate to its composition and structure14. To

investigate the structure and composition of materials, analytical tools and

techniques are employed. The microscope ranks top among such analytical

tools, and microscopy is an indispensable analytical technique.

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1.2.1 LEVELS OF STRUCTURE

The internal structure of a material, simply called the structure, can be

studied at various levels of observation. The magnification and resolution of

the physical aid used are a measure of the level of the observation. The

higher is the magnification, the finer is the level. The details that are

disclosed at a certain level of observation are generally different from the

details disclosed at some other level1, 15. Depending on the level, we can

classify the structure of materials as: macrostructure, microstructure, sub-

microstructure, crystal structure, electronic structure, and nuclear structure.

Macrostructure of a material is examined with the naked (unaided) eye or

under a low magnification, e.g. a hand lens. Standard procedures of macro-

examination reveal flaws and segregation in a material.

Microstructure generally refers to the structure as observed under the

optical or light microscope. This microscope can magnify a structure up to

about 1500 times linear, without loss of resolution of details of the structure.

The limit of resolution of the human eye is about 0.3mm, that is, the eye can

distinguish two lines as separate lines, only when their distance of separation

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is more than 0.3mm. The optical microscope can resolve details up to a limit

of about 0.1µm (100nm or 0.0001mm).

Substructure or sub-microstructure refers to the structure obtained by

using a microscope with a much higher magnification and resolution than

the optical microscope. In an electron microscope, a magnification of 1, 000,

000 times linear is possible. By virtue of the smaller wavelength of electron

waves as compared to visible light, the resolving power also increases

correspondingly, so that much finer details show up in the electron

microscope. We can obtain a wealth of additional information on very fine

particles or on crystal imperfections such as dislocations. The electron

diffraction patterns obtained along with the photograph of the substructure

greatly aid in understanding the processes taking place in materials on such a

minute scale. NB: The term ‘microstructure’ is used quite often in technical

literature to mean both microstructure and sub-microstructure. This usage

shall be followed in this term paper.

Crystal structure tells us the details of the atomic arrangements within a

grain or crystal of a material. It is usually sufficient to describe the

arrangement of a few atoms within what is called a unit cell. The crystal

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consists of a very large number of unit cells forming regularly repeating

patterns in space i.e. three dimensions. The main technique employed for

determining the crystal structure is the x-ray diffraction.

Electronic structure (part of atomic structure) of a solid usually refers to

the arrangement of electrons in the shells and orbitals of individual atoms

that constitute the solid. Spectroscopic techniques are very useful in

determining the electronic structure.

Nuclear structure (another part of atomic structure) reveals the

arrangement of protons and neutrons in the atomic nucleus. It is studied by

nuclear spectroscopic techniques, such as nuclear magnetic resonance

(NMR) and MÖssbauer studies.

1.2.2 METHODS OF STRUCTURAL AND COMPOSITIONAL

ELUCIDATION

The science of materials uses diverse methods for the testing and analysis of

materials to obtain exhaustive and reliable information on the properties

depending on the composition, structure, and processing of the materials

being studied11. With the great diversity of instrumentation available today,

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the role of the traditional analytical laboratory has now been expanded to

include determinations of morphology, microstructure, crystallography and a

variety of physical properties. The term often associated with the

combination of analytical chemistry techniques and these other methods of

analysis is materials characterization.2, 14


Not only have the variety of

materials and the types of instrumentation available increased, but the

reasons for looking at these materials have also multiplied. The demand for

materials with unique properties grows on daily basis, and so also does the

complexity of the materials themselves and the methods needed to analyze

them.

The numerous methods, which may differ substantially from one another,

may be divided into two large groups as follows:

1. Methods for determining the structure and structural transformations

in materials. These in turn should be classed into:

 Direct methods for examining and determining the structure of

materials; they are termed structural methods and include

macroscopic examination or macro-analysis, microscopic

examination (microanalysis), and x-ray examination.

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 Indirect methods based on certain relationships existing

between the structure and properties of materials; they can

provide quite reliable data on the structural transformations

occurring in metals during their treatment or service condition

by measuring the variations of their physical properties e.g.

thermal analysis (for enthalpy changes), dilatometric analysis

(for linear and volumetric thermal expansion), and various

analytic techniques for electrical resistance, saturation

magnetization, and some chemical and mechanical properties.

2. Direct methods for determining the properties of materials as required

by certain operational conditions, in the first place their mechanical

properties, and also physical and chemical properties.

1.2.3 MICROSCOPY

Microscopic examination (microanalysis) is the study of the structure of

materials under microscope at large magnifications. Depending on the

magnification required the phases of a structure, their number, shape and

distribution may be studied by using visible light beam, electron beam, or

any other electromagnetic radiation that may result from the interaction of

electrons with the material under study.

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A. OPTICAL MICROSCOPY

The metallurgical microscope is an optical microscope designed for use in

the study of metals, and their alloys. It enables opaque objects to be seen

with a certain magnification in reflected light. A metallurgical microscope

comprises an optical system (lenses, prisms, and mirrors), illuminating

system (including a light source, lenses, light filters, diaphragms, and a

photographic camera), and mechanical system (stand, tube and stage –

where the micro-section or specimen is placed).

Different magnifications can be obtained by changing the combinations of

glass lenses and prisms. The useful magnification, however, cannot exceed

1500 because of light diffraction. With such a magnification it is possible to

detect elements of a structure not less than 0.2µm in size, which is in most

cases sufficient for determination of the majority of phases present in an

alloy.

Optical microscopy can be used to achieve the following:

 Determination of phase composition and structure of alloys in

equilibrium, e.g. in castings and annealed components.

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 Determination of non-equilibrium structures, e.g. structures resulting

from rapid cooling or quenching.

 Determination of the method of metal treatment and the effect of such

processing methods on the structure, e.g. casting, plastic working,

welding, heat treatment, etc.

 Quantitative metallography, e.g. determination of grain size, size of

inclusions, and phase distribution in a material.10

B. ELECTRON MICROSCOPY

In the electron microscope, electron beams and an electron-optical systems

consisting of electromagnetic and electrostatic lenses are used instead of

light beam and glass lenses. The wavelength of electrons is inversely

proportional to their momentum. Thus, it is possible to change (reduce) the

wavelength by varying (increasing) the velocity of electrons, by passing

them through an electric field of high intensity which accelerates them. It

follows that the lower the wavelength, the better the resolving power

achievable.

The resolving power feasible in an electron microscope is 100 000 times that

attainable in an optical microscope. However, because of various

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phenomena accompanying the passage of a stream of electrons, e.g.

spherical and chromatic aberrations, etc, the maximum useful resolving

power of an electron microscope is actually only 100 – 200 times greater

than that of optical microscopes. Thus, the maximum magnification that can

be realized in an electron microscope is 100 000 to 200 000 times linear.

According to the method in which the object is examined by means of

electron beams, the following basic types of electron microscope exist:

 Transmission Electron Microscope (TEM) in which the stream of

electrons passes through the object, the image formed being the result

of different scattering of electrons by the object;

 Scanning Electron Microscope (SEM) wherein the image is produced

from the secondary emission of electrons emitted by the surface being

scanned by a stream of primary electrons;

 Scanning Transmission Electron Microscope (STEM) which marries

the SEM and the TEM, i.e. it is a hybrid of the two basic types of

electron microscopes.

This term paper shall be concerned with the application of electron

microscope techniques to the general study of solid matter in the physical

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sciences. The range of materials that is susceptible to these probing

techniques is very wide, encompassing metals, semiconductors, minerals,

fibres and amorphous structures.12

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CHAPTER TWO

2.0 TRANSMISSION ELECTRON MICROSCOPY

2.1 INTERACTION OF ELECTRONS WITH SOLIDS

Different kinds of electrons and electromagnetic waves are emitted from a

specimen irradiated with high-energy or high-speed electrons,9, 12, 17


the

different waves resulting from elastic or inelastic scattering processes. In

elastic scattering the path or trajectory of the moving electron is changed,

but its energy or velocity is not altered significantly. Inelastic scattering

occurs when the moving electron losses some of its kinetic energy as a result

of its interaction with the specimen.

The different signals are used in different microscopes and for different

imaging modes. Information on the crystal structure and on defects in the

specimen can be obtained by studying the elastically scattered electrons

whereas investigations of in-elastically scattered electrons and of other

waves leaving the specimen allow the determination of chemical

composition and topology of the specimen surface.

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2.2 TRANSMISSION ELECTRON MICROSCOPE (TEM)

The development of the TEM provided a powerful technique for

metallurgists or materials scientists / engineers to study the internal structure

of thin crystalline films or foils. The conventional or standard mode uses the

transmitted beam coming out of the specimen; hence the name –

transmission electron microscopy. The objects to be examined in a

transmission microscope must be transparent to electrons, i.e. their thickness

must be very small so that electron waves can pass through. They are usually

made in form of thin metallic films (100 - 2000Ǻ thick) or replicas (moulds)

of the surface of a metallic micro-section.

This can be used both to investigate the internal defect structure of a

crystalline specimen using the instrument as a microscope, and to determine

a considerable degree of information about the crystallographic features of

the specimen using it as a diffraction instrument. Normally, when an

electron beam strikes the specimen, part of the beam is diffracted by the

crystal planes in the material, and the remainder will pass directly through

the specimen without being diffracted.

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In operating the instrument as a microscope, one has the choice of using

either the image formed by the direct or transmitted beam or the image

formed by the diffracted beam. The TEM is so constructed that either of the

images can be viewed on the fluorescent screen of the instrument, or be

photographed on a plate or film.

When the diffracted beam is intercepted [by a diaphragm in the optical path

of the TEM], while the transmitted beam is allowed to pass through the

aperture, the image formed is said to be a bright-field (BF) image.

Imperfections in the crystal normally appear as dark areas in a BF image.

These imperfections could be small inclusions of different transparency from

the matrix crystal and therefore visible in the image as a result of loss in

intensity of the beam where it passes through the more opaque particles. Of

more general interest, however, is the case where imperfections are faults in

the crystal lattice itself, e.g. dislocations. Because these imperfections cause

diffraction of the beam, they are visible in the image formed by a direct or

transmitted beam. In a bright-field image, dislocations normally appear as

dark lines.

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The alternate method of using the electron microscope [i.e. using it as a

diffractometer] is to place the aperture so that a diffracted ray is allowed to

pass, while the transmitted beam is cut off. The image of the specimen

formed in this case is known as the dark-field (DF) image. Here,

dislocations appear as white lines lying on a dark background. Also, a

diffraction pattern is obtained whose spots correspond to the planes of the

zone that has its axis parallel to the electron beam. The diffraction patterns

can yield information both about the nature of the crystal structure (bcc, fcc,

hcp, etc) and about the orientation of the crystals in a specimen.

Furthermore, the TEM has a diaphragm in its optical path that controls the

size of the area that is able to contribute to the diffraction pattern. As a

result, it is possible to obtain information about an area of specimen that has

a radius as small as 0.5µm. The diffraction patterns are therefore called

selected area diffraction patterns.

2.3 TEM MODES AND APPLICATIONS

The TEM can be operated in different modes. In the standard mode or

conventional transmission electron microscopy (CTEM) mode, the

microscope is operated to form images by bright field (BF), dark field (DF),

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or lattice image (phase) contrast. A lattice image or phase contrast is

formed by the interference of at least two beams in the image plane of the

objective lens. In the scanning mode, the TEM is used as a SEM i.e.

scanning transmission electron microscopy (STEM) mode. However, this

section shall be concerned with the conventional mode.

2.3.1 GENERAL

In most cases the TEM can be used to derive information of several different

kinds which extend right across the sciences concerned with elucidating

microstructure. The external surface of a body can be studied and

information obtained concerning the external morphology of the specimen

and also microscopic details of the surface roughness can be investigated.

Materials of interest here are fibres and small particles in which the natural

surface has a direct bearing on the properties and uses of the material.

However, even in materials in which surface properties are not important

much information about the constitution of the material can be achieved by

studying a prepared surface. The TEM may be used to cast a shadow of the

specimen (shadow microscopy), if it is sufficiently small, or to observe a

replica of the specimen surface. Information about the internal structure of a

material is obtained directly in transmission.

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2.3.2 SURFACE INFORMATION & EXTERNAL MORPHOLOGY

One of the first applications of the TEM was to study the size, shape and

dispersion (distribution) of small particles. Here, of course, transmission of

electrons is not essential and the microscope is used as a super optical

microscope of great magnifying power. Shadow micrographs of particles

and fibres show the shape of the object and, if the specimen preparation is

well controlled, a typical state of dispersion of the particles. Important

applications in this area are the study of particle shape and size distribution

from

 Solutions such as colloidal preparations, soil fractions and

precipitates, e.g. in colloid and surface chemistry, mineral processing

and hydro-metallurgy, ceramics particulate materials processing;

 ‘Dry’ origins such as airborne dusts, paint pigments, powders and

fibres, e.g. in powder metallurgy, cement production, polymer and

textile processing, etc.

If the specimen has a characteristic shape, such as that possessed by certain

minerals and viruses, a study by electron microscopy can be an aid to

identification. An added bonus of crystal structure identification by electron

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diffraction is obtained if crystalline particles occur naturally as thin platelets

or are produced in thin form.

2.3.3 CONTRAST FROM AN IMPERFECT CRYSTAL

For a perfect single crystal, uniform intensity is expected in any particular

image. However, crystalline materials are not void of defects or

imperfections. A necessary requirement in microscopy is, of course, the

observation of changes in intensity or the presence of contrast as this is the

only way of detecting structural information. The presence of defects that

are of an effective size greater than the resolving power of the TEM can, in

principle, be detected by changes in contrast that result from differences in

electron scattering power between the defect and the surrounding perfect

lattice of atoms.

Perhaps the lattice defect most often studied in transmission electron

microscopy is the dislocation. This defect is important because it is related

to other properties of materials such as mechanical and electrical properties.

Contrast conditions in transmission electron microscopy are employed in the

study of line and planer defects. Information can be obtained about partial

dislocations and the interaction of dislocations in deformed material. The

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crystallographic nature and origin of the important line defects known as

dislocation loops can also be determined.

Dislocation loops can be formed during work hardening and deformation

processes, in quenched materials and as a result of irradiation damage. They

result from interaction mechanisms in long dislocation lines or from the

condensation of point defects. The nature of these loops i.e. whether they are

vacancy (formed from a condensation of vacancies) or interstitial (formed

from interstitial atoms) can be determined by fairly straight forward contrast

techniques. Transmission electron microscopy has, in recent years, played an

important role in characterizing the nature of irradiation damage in materials

used in nuclear reactor technology.

Dislocation densities can be computed from electron micrographs as long as

the crystal or foil thickness is known so that a true volume count can be

obtained. Slip planes or twinning planes can be characterized and the nature

of stacking faults can also be investigated by routine contrast analysis.

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2.3.4 PRECIPITATES AND SECOND PHASES

A major area of interest in materials science is the study of precipitation

phenomena in the solid state and the structure of multiphase materials. A

second phase often has a dramatic effect on the physical properties of a

material and is often at the size level too small to allow an examination by

optical techniques. Hence, electron microscopy is used to study these

precipitates and second phase particles. This could comprise, for example,

studies of precipitate identity, crystal structure, morphology, the kinetics of

precipitation, precipitate sizes and dispersions and interfacial effects such as

the problem of coherency and the characteristics of interfacial dislocations.

Interfacial dislocations also occur in composites where a composite structure

of several phases is created by solid state reactions or mechanical methods.

In the later class (composites formed by mechanical methods), of course, the

materials are often non-crystalline e.g. glass and carbon fiber material and

polymers.

2.3.5 SPECIALIZED TECHNIQUES OF TEM

Several relatively new and often specialized techniques of transmission

electron microscopy have been developed. They are techniques or modes of

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operation of the conventional TEM that yield useful information but have, a

rather narrow, application to a particular phenomenon or class of materials.

 An important development in the study of defects in crystals at high

resolution is the application of dark field techniques and the use of

‘weak beam’ conditions. Application to stacking fault energy

determination from the separation of partial dislocations bounding the

fault is an obvious example for this technique and so is the study of

stress fields at the interface of different phases.6, 12

 The fringes observed in the images of stacking faults are often termed

α-fringes. Other types of defect or deformation can introduce fringes

into the electron micrograph image and the origin of the fringe pattern

is often complicated, and there is need to investigate it. Fringe

systems are dependent on their imaging conditions and often behave

differently in bright and dark field settings. It is clear therefore that

the observation of a fringe system or boundary in the image of a

crystalline material does not imply the existence of a simple stacking

fault, grain boundary or wedge. In other words, it is not every fringe

that is an α-fringe -- originating from the relative displacement of

identical parts of the crystal.

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Special techniques of the TEM have shown that anti-phase boundaries

(A.P.B’s) in such systems as ordered Cu3Au and domain boundaries

in ferroelectric and some anti-ferromagnetic crystals are a source of

such fringes.

 Specialized techniques of the TEM can be used to reveal phase

contrast. Two important examples of phase contrast microscopy are in

the imaging of structural detail approaching atomic dimensions and

magnetic structure. Magnetic contrast is revealed by defocusing the

objective lens and taking the distribution of electron intensity at a

distance above or below the specimen as the object. At large

defocusing distances recognizable interference patterns occur and it is

possible to use these patterns to investigate the detailed magnetic

structure inside domain boundaries. Lorentz microscopy, as this

technique has come to be known, enjoys applications in the

elucidation of domain structures at high resolution in such technically

important materials as those used in magnetic memory and logic areas

in computer technology. One of these applications is in research into

the magnetic properties of materials supporting a type of domain

known as the magnetic ‘bubble’ domain. These cylindrical domains

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are mobile and can be used to represent information in a binary code,

e.g. the presence of bubble signifies unity and its absence zero.

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CHAPTER THREE

3.0 SCANNING ELECTRON MICROSCOPY

3.1 SCANNING ELECTRON MICROSCOPE (SEM)

The scanning electron microscope (SEM) can be considered as an

instrument that greatly extends the usefulness of the optical microscope for

studying specimens that require higher magnifications and greater depths of

field than can be attained optically. The SEM is capable of greatly extending

the limited magnification range of the optical microscope beyond 1500x to

over 50 000x. Functionally, it should be the natural successor to the optical

microscope, but historically, the TEM came earlier.

A SEM has a lower resolution than a TEM, but its advantage is that the

structure of the surface of an object can be examined directly, i.e. without

making replicas or thin foils. Scanning electron microscopy has provided us

with many new data and extended our knowledge of peculiarities of the fine

structure of materials, the structure of ageing alloys, and the structures of

isothermal transformations in super-cooled austenite, etc. In addition, it is

possible to obtain useful images of specimens that have a great deal of

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surface relief such as are found on deeply etched specimens or on fracture

surfaces. The depth of field of the SEM can be as great as 300 times that of

the optical microscope. This feature makes the SEM especially valuable for

analyzing fractures.11, 17

On the other hand, at low magnifications, that is, below 300 to 400x, the

image formed by the SEM is normally inferior to that of an optical

microscope. Thus, the optical and scanning microscopes can be viewed as

complementing each other. The optical microscope is the superior

instrument at low magnifications with relatively flat surfaces and the

scanning microscope is superior at higher magnifications and with surfaces

having a strong relief.

In the SEM, the image is developed as in a television set. The specimen

surface is scanned by a pointed electron beam over an area known as the

raster. The interaction of this sharply pointed beam with the specimen

surface causes several types of energetic emissions, including back-scattered

or reflected electrons, secondary emitted electrons, Auger electron (a special

form of secondary electrons), continuous and characteristic x-rays, etc. Most

of these emissions/radiations [when collected by a detector and focused] can

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furnish useful information about the nature of the specimen at the spot under

the beam. In the standard mode of the SEM, one normally uses the

secondary electrons to develop an image. The reason for this is that the

secondary electron signal comes primarily from the area directly under the

beam and thus furnishes an image with a very high resolution or one in

which the detail is better revealed.

The typical SEM uses 1000 line scans to form a 10 x 10cm image. A CRT

(cathode ray tube) screen with a long persistence phosphor is used so that the

image will last long enough for the eye to be able to see a complete picture

without problems of fading. The complete scanning process is repeated

every thirtieth of a second, which conforms well to the one-twenty-fourth of

a second frame time of a motion picture. To obtain a permanent

photographic record of the image, on the other hand, a cathode ray tube with

a short persistence phosphor is used. This avoids overlapping of images

from adjacent lines.17

3.2 SEM MODES AND APPLICATIONS

The field of application of scanning microscopy is wide indeed, and the

requirements for suitable specimens are much less stringent than for

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transmission microscopy. With the SEM, virtually anything that does not

decompose or collapse in the beam or the vacuum of the instrument can be

examined using emissive effects. The SEM may utilize any of a number of

different types of signal [reflected or backscattered electrons, secondary

emitted electrons, light photons (cathodoluminescence), x-ray photons,

Auger electrons, transmitted electrons, conducted specimen currents, and

absorbed specimen currents] to produce an image from a specimen. In each

case the microscope will be employed in a particular operating mode.

3.2.1 THE REFLECTIVEAND EMISSIVE MODES

These modes are closely related. The reflective mode uses reflected or

backscattered electrons while the emissive mode makes use of secondary

emitted electrons. They can be used to reveal a lot of information as

discussed below.

A. TOPOGRAPHIC AND ATOMIC NUMBER CONTRAST

The characteristics of both reflected and secondary electrons are sensitive to

variations in atomic number (hence composition) and topography. However

the reflective mode is much more efficient in detecting atomic number

contrast while the emissive mode is used when topographical information is

required.

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The majority of observations undertaken with the SEM exploit the

topographic contrast provided by the emissive mode. Hence, this is the

conventional application of scanning microscopy. Any aspect of materials

science that is concerned with surfaces is likely to benefit from the emissive

mode of scanning microscopy. Particular examples in metallurgy are

precipitate morphology and fractography. Micrographs of fractured surfaces

for example, can reveal the presence or not of intergranular and

transgranular cracking. Also, fracture planes may be identified if

characteristic angles can be observed.

The advantages of scanning microscopy in the study of fibres, textile and

polymers were recognized at an early stage. On account of the fragility and

non-planar nature of these materials, other methods of observation are much

more difficult. The types of problem associated with textile research include

the determination of the size distribution of constituent fibres and the study

of the deleterious effects of washing, wearing and dyeing processes on

fabrics. An added bonus of the SEM is that the large specimen chamber

allows the possibility of dynamic experiments in stretching and fracture

studies.

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B. ELECTRIC AND MAGNETIC FIELD CONTRAST

Important contrast effects in the emissive mode arise from the presence of

external electric or magnetic fields above the specimen surface. In both

cases the trajectories of the secondary electrons are altered by the electric

fields and clearly observed contrast may be obtained. Interesting results of

the application of field contrast techniques are found in the study of

magnetic domains.

C. VOLTAGE (POTENTIAL) CONTRAST

This is another contrast effect observable in the emissive mode and one

which is particularly valuable in the study of semiconducting materials. The

best results seem to be obtained for untilted specimens and a low

accelerating voltage for the microscope. The lower the voltage at a particular

specimen area the brighter will be the corresponding area in the CRT image.

The most widespread use of voltage contrast is found in the examination of

semiconducting materials and devices e.g. the p-n junction. If a p-n junction

with reverse bias is mounted in the microscope the p and n type material will

be at different voltages and thus the junction region is revealed. The location

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of the junction in this simple way is often a prelude to the performance of

more complicated experiments in the conductive mode. Apart from the

simple p-n diode, voltage contrast can be obtained in transistor and

integrated microcircuits. Here the advantage of the SEM is that it will

provide information about the device under actual operating conditions and

allow its performance to be checked. The frequency dependent

characteristics of these devices are studied using stroboscopic techniques.

D. ELECTRON CHANNELLING PATTERNS (ECP’s)

Electron channeling effects are one of the growth points of scanning

microscopy because of the valuable crystallographic information they yield.

Although the reflective mode is often used to detect channeling patterns they

can also be seen in the emissive and absorptive modes. Moreover a

photographic film suitably placed in the vicinity of the specimen will record

a ‘channeling type’ pattern if the scan generator is switched off. The term

ECP (Electron Channeling Pattern) arises because the channeling effect

essentially causes a dependence of the backscattered signal on the angle

mode by the incident beam to the lattice and so produces contrast.

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Channeling patterns have very useful properties relating to the fact that they

depend upon the crystallography of the specimen. The angular width of any

band is 2θ and so depends not only on crystal properties i.e. interplanar or‘d’

spacings but also upon the accelerating voltage which controls the electron

wavelength. If V is known accurately then measurement of 2θ yield the‘d’

spacings and hence the lattice constants. Lateral movement of the specimen

causes no change in the ECP but a tilt or rotation will produce change, a

property shared with Kikuchi patterns seen in the conventional TEM. Hence,

ECPs are sometimes referred to as pseudo-kikuchi lines. By progressive

tilting of the specimen in various directions an ECP map corresponding to

the stereographic triangle can be constructed, and consequently the

crystallographic orientation of the specimen can be determined. Where the

pattern contains a low index pole it may be solved by inspection.

Apart from instrumental factors, the quality of ECP’s depends upon the

perfection of the crystalline sample and this property has been exploited in

various applications of the technique e.g. studies of in situ deformation and

effects of radiation damage. Under certain circumstances grain contrast can

be obtained from polished polycrystalline specimens, a situation which

yields direct information about the size distribution of constituent

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crystallites. The microscope conditions required to obtain grain contrast are

similar to those suitable for the observation of ECP’s. Selected area

channeling patterns can be used to determine the crystallographic orientation

of individual grains. And the density of lattice defects at particular specimen

locations can be evaluated.

3.2.2 ABSORPTIVE MODE

Absorbed currents will flow if an electrical lead is connected between an

illuminated specimen and earth. This specimen absorbed current is the

difference between the primary current (incident electron beam) and the sum

of secondary and reflected currents/beams. The information gained from the

absorptive mode is largely complementary to that provided by the reflective

and emissive modes operation. However compositional variations are

enhanced at the expense of surface topography. The absorptive mode should

not be confused with the widely used conductive mode which exploits

induced conductivity in semiconducting materials.

3.2.3 CONDUCTIVE MODE

Electron beam induced conductivity has proved of great value in the

investigation of semiconducting materials and is often used in conjunction

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with voltage contrast obtained in the emissive mode. The basis of the

technique is the production of electron-hole pairs by the beam, i.e. the

excitation of electrons from the valence to the conduction band which

thereby leave the holes. The process of charge separation with its resulting

effect in an external circuit is often known as charge collection and the

current produced as the charge collection current. Generally speaking those

areas in which efficient charge collection occurs appear correspondingly

bright in the image.

Two types of problem can be tackled with the conductive mode of scanning

microscopy. In the first, the variation in charge collection current is used to

probe structural features of the specimens. In the second, the behaviour of

semiconductor devices such as diodes and field effect transistors (FETs) can

be examined under various working conditions. In this way the microscope

is used as a diagnostic tool to detect possible faults and breakdowns in

devices. Certain electrical measurements can also be made.

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3.2.4 LUMINESCENT MODE

Cathodoluminescence (CL) is a phenomenon which occurs in a great variety

of materials ranging from biological specimens to semiconductors and

minerals. CL signals can only be obtained if:

 The material under examination is transparent to the radiation being

collected and total internal reflection does not constitute a barrier to

escaping radiation;

 The dwell time of the probe at any point on the sample is greater than

the relaxation time for the luminescent process otherwise blurring of

the image will occur.

The fact that cathodoluminescent intensity is strongly sensitive to impurities

and irregularities in a sample is of considerable benefit to the user of the

SEM in the luminescent mode. By taking sequential micrographs in the

emissive and luminescent modes the catholuminescent centres within a

sample can be identified with features of the physical structure such as

damage, defects or polytypic bands. By allowing some of the reflected

primaries to reach the collector, a composite image can be obtained which

gives luminescent as well as topographical information.

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The link between impurities and luminescent centres has been widely

utilized in the study of semiconducting materials. A case is the investigation

of the relevance of dopant concentration in the manufacture of

semiconductors. A good example is the investigation of czochralski-grown

crystals of laser quality GaAs heavily doped with Te atoms.12

3.2.5 X-RAY AND AUGER MODES

The SEM can be easily converted in to an instrument capable of chemically

microanalyzing specimens. X-rays and Auger electrons can be analyzed to

reveal information by x-ray microanalysis and Auger electron spectroscopy.

a) The electron probe microanalyzer uses the characteristic peaks of

the x-ray spectrum resulting from the bombardment of the specimen

by the beam electrons. An electron probe microanalyzer is thus

basically an SEM equipped with x-ray detectors. Two basic types of

detectors are used. In the energy- dispersive (ED) x-ray

spectrometer, a solid-state detector develops a histogram showing

the relative frequency of the x-ray photons as a function of their

energy. In the wavelength – dispersive (WD) method a crystal

spectrometer is used to disperse the emerging x-rays in such a way

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that only photons of selected wavelength (those fulfilling the Bragg

law) reach a counter. There is a tendency for reasons of speed and

convenience to favour the use of ED techniques in SEM

applications.

Various types of output signal are possible in the x-ray mode in

either ED or WD systems. An x-ray image can be thrown on to the

video CRT by choosing a particular x-ray wavelength or energy. The

location of the element possessing this characteristic wavelength

will be revealed as bright contrast image. A modification allows

similar information to show on a line scan. Alternatively the electron

probe may be focused on a spot to provide a point analysis. The

whole range of x-rays can be collected and analyzed to allow

identification of the region in question. In addition to identification

of elements determination of the concentration of an alloy

component at a point is also possible.

The electron microprobe is a useful instrument for the identification

of the various phases in a metal specimen, including the non metallic

inclusions found in almost all commercial metals. Another area

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where this instrument has proven valuable is in diffusion studies

where information about composition gradients is required. It can

also be used to prove whether or not \a metal alloy has a

homogenous composition.

b) There are difficulties associated with the detection of low atomic

number elements for which the x – rays have low energies and long

wavelengths. Although the crystal spectrometer can cope, another

technique used for the analysis of low atomic number materials (Z

<11) is that of Auger Spectroscopy. When an Auger electron is

ejected from an atom, it leaves with a fixed amount of kinetic

energy.

A significant feature of the Auger reaction is that it involves three

electrons: the electron knocked out of an inner shell, the outer – shell

electron that jumps into the inner – shell hole, and the ejected outer

– shell electron (the Auger electron). It is common practice to

describe a particular Auger reaction with a three – letter symbol

identifying the three basic types of electron energy levels involved

in the transition, e.g. KLL, MNN, and LMM.

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One cannot perform an Auger analysis for an element having less

than three electrons because three electrons are needed for an Auger

transition. This eliminates hydrogen and helium from consideration.

An Auger analysis is normally based on measurement of the

strengths of the Auger peaks in a plot of the back scattered electron

energy per unit energy interval (ε) versus the energy of the electrons

(E).

The Auger electron spectrum is displayed using a suitable detection

system and thus compositional analysis can be done. As with x –

rays a particular Auger electron energy can be chosen to display a

distribution map on the video CRT.

In summary, Auger electron spectroscopy is useful for determining

the compositions of surface layers to a depth of about 2nm for

elements above He. It also has a spatial resolution > 100nm, which

is about is about a tenth of that of the electron probe x – ray micro-

analyzer. This makes this technique well suited to the studies of

grain boundaries in metals and alloys, especially with specimens

susceptible to brittle grain boundary fractures. It is also useful for

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surface segregation studies as in the solving of stress – corrosion

problem. 12, 17

3.3 EXPLOITING THE VERSATILITY OF SEM

As far as applications are concerned the SEM is an instrument endowed with

considerable versatility. Unfortunately, the instrument is sometimes under –

utilized by relying heavily on the conventional mode (topographic contrast

of the emissive mode). When tackling a particular problem therefore it is

prudent to consider what extra information might be gained in other

accessible modes. The information obtained with scanning microscopy may

be broadly categorized into four, viz;

(i) structural and topographical,

(ii) chemical or compositional,

(iii) crystallographic,

(iv) electrical and magnetic .

As a result of recent developments the emissive and reflective modes render

possible the direct observation of magnetic domain structures in a great

range of materials. Moreover the method has certain advantages over more

traditional techniques e.g. it can reveal the internal domain structure. Apart

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from the domain patterns themselves the probe may be used to investigate

the field distributions from recording tapes and heads. As far as electrical

properties are concerned the emissive mode signals is sensitive to and

distinguish between surface field and surface voltage. Variations in these

quantities are therefore made visible in circuits and devices.

Success in the use of all the modes of the SEM came as a result of

improvement in signal processing, signal processing increases the signal to

noise ratio, thus improving contrast generally, and discriminates between

signals from different sources. 12

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CHAPTER FOUR

4.0 THE STEM AND OTHER DEVELOPMENTS

4.1 SCANNING TRANSMISSION ELECTRON MICROSCOPE

The disadvantage of the SEM is its comparatively poor resolution which in

ordinary imaging mode nowhere approaches that of the conventional TEM.

The attraction of marrying the resolution of the TEM with the versatility and

signal processing of the SEM is obvious and this explains the growing

interest in scanning transmission microscopy. The scanning transmission

electron microscope (STEM) is so named because it combines features of

the two basic types of electron microscopes.

Essentially, the STEM consists of a series of lenses which focuses a probe

on to the specimen which is them scanned in the usual way. Unlike the

normal SEM modes however, the specimen is made sufficiently thin to

allow the transmission of electrons. After transmission these are detected

and the signals amplified and displayed for analysis. 12

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4.2 APPLICATIONS OF THE STEM

Since its early development in the late 1960’s by a group in Chicago, the

dedicated STEM has established itself as a powerful instrument for high

resolution imaging, as clearly evidenced by the visualization of individual

atoms and molecules. Another group in Arizona emphasized the impact of

the STEM for the structural analysis of crystalline objects. They pointed out

its capabilities for delivering much localized structural information, because

it provides a convergent beam electron diffraction pattern from each point on

the specimen. 7

STEM instrument have proved to be the most efficient category of analytical

electron microscopes, pushing the limits of sensitivity of the identification,

by use of electron energy loss spectroscopy (EELS), to typically ten atoms.

[EELS is applied mainly to ceramic specimens since it is the only technique

for the determination of the distribution of light elements. Ion implantation

is sometimes employed to introduce light – element dopants into

semiconductors. EELS could be used to measure local dopant

concentrations, if the latter exceed ~ 0.1%. Light elements occur in certain

metal specimens in the form of nitrides or carbide precipitates; these

materials have also been analyzed by the EELS technique]. When equipped

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with different analytical devices such as an energy dispersive x - ray detector

(EDX), a cathodoluminescence detector and an Auger detector, the STEM

constitutes an extremely powerful tool for microanalysis and its impact into

the microelectronic age has been noted. All aspects of its performance rely

on the “nanoprobe”.7

The future trend of the STEM is that of eclipsing the conventional TEM and

becoming an all-embracing multipurpose electron microscope.12

4.3 HIGH RESOLUTION STEM

Certain research groups and commercial manufacturers have pursued the

goal of designing a high resolution STEM, i.e. a device which will match the

resolution of a good conventional TEM. Incorporated with an energy

analyzer, this instrument and technique has been used to observe single

atoms of heavy elements. There is also the possibility of imaging unstrained

biological molecules and obtaining better resolved images of

crystallographic defects.12

4.4 THE TEM AT HIGH VOLTAGES

A high voltage electron microscope (HVEM) can be defined as one working

at and above 500kV. Most high voltage instrument in operation at the

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present time work at voltages up to 1MV, and some are designed to use

electron beams with energy up to 3MeV or even 10MeV.

The motivation for going to high voltages is to achieve increased

transparency. Increased penetration of the electrons should enable thicker

specimens to be observed in transmission. Also, the decrease in electron

wavelengths should lead to better resolution. The possibility of using thicker

specimens is extremely important in some materials science applications

where it is clear that many defects structures and dynamic processes in very

thin sections are not typical of the bulk material.

High voltage electron microscopy has found applications in many problems

of materials science. The major interest areas are:

 The utilization of thick specimens for studies of defects and ‘difficult’

materials and for structure-related, in situ dynamic experiments,

 Experimentation with ‘environmental cells’ to reproduce for example

surface chemical reactions with the intention of studying the kinetics

and products of the reaction in microscopic detail and,

 To take advantage of features peculiar to the HVEM such as the

energetic electron beam for radiation damage studies.

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The terminology ‘difficult specimens’ applies to materials from which it is

difficult to make good TEM specimens suitable for ordinary voltage

(100kV) microscopy. Also, the term ‘environmental cells’ implies that the

specimens are kept in their normal environment whilst under observation.

A wide application to corrosion metallurgy, catalysis studies and surface

physics and chemistry abound in the use of environment cells for high

voltage electron microscopy. With the design of efficient environmental

cells the life sciences will also benefit. The design of successful and

economic nuclear power reactors and piles depends on knowledge of the

radiation damage sustained by the materials making up the fabric of the

reactor itself. High voltage electron microscopy is exploited in the

experimental study of such effects.12

4.5 ANALYTICAL TEM

We have already considered the incorporation of x-ray microanalysis

facilities into the SEM. Similar techniques can also be combined with the

conventional TEM. One of such analytical transmission electron

microscopes is the EMMA- 4. This instrument is said to probably have the

highest spectral resolution of any commercial machine available.

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The great advantage of an analytical microscope is that it allows a

correlation of chemical composition with microscopic detail and diffraction

data on a very fine scale. For this reason it is ideally suited to a whole range

of biological and materials science problems where small concentrations of a

minority element or precipitation are concerned.

4.6 ENERGY ANALYSING MICROSCOPES

The discussion of energy analysis occupies a place in the rapidly growing

field of electron spectroscopy. It is becoming a specialized research tool

fitted to the new STEM class of microscopes. Energy analyzers have also

been fitted to the conventional TEM in order to obtain information from

inelastically scattered electrons which otherwise would be lost.

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CHAPTER FIVE

5.0 SPECIAL TECHNIQUES OF SURFACE MICROSCOPY AND

ANALYSIS

5.1 INTRODUCTION

In addition to light microscopy and transmission and scanning electron

microscopy used routinely in all fields of materials research, development

and control, microstructures can be investigated by several more exotic

image techniques. While some of these, such as photoemission or field-ion

microscopy, are of high interest for various advanced studies of material

surfaces, others are still in the stage of experimentation, have been

substituted by other techniques or are more useful in other fields of

application like biology or mineralogy.

Instruments capable of analyzing the chemical nature and the electronic state

of surface atoms have been developed at a rapid rate in the last few years,

utilizing all kinds of interaction with incident photons, electrons and ions.

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5.2 ACOUSTIC AND THERMAL WAVE IMAGING

 The acoustic microscope is a rather new development. A

piezoelectric crystal is attached to the sample, which emits acoustic

signals and after reflection at the surface, transforms them back to an

electric signal. This signal writes the image on a CRT. The

information furnished by the acoustic microscope is different from

that furnished by optical microscopes and scanning electron

microscopes in that it reveals sub-surface defects like grain

boundaries. The most recent development is the scanning acoustic

microscopy (SAM).

Macroscopic and microscopic features on the surface or close to it can

be imaged using the dependence of the photo-acoustic effect on local

variations of the thermal properties of a material (density, specific

heat, and conductivity). This new technique, not only offers sensitive

detection of minor as well as more substantial disruptions of the

lattice structure (as for example, foreign atoms in concentrations

below 10-3, vacancies, compositional changes, mechanical defects) but

also a means for nondestructive depth profiling.

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 In a thermal – wave microscope, an electron beam (or a laser beam)

is focused and scanned across the surface of a sample. Periodic

surface heating results as the beam intensity is modulated in the range

of 10Hz – 10MHz. Thus, thermal waves are produced which interact

with features. Reflected and scattered waves are detected by

monitoring local surface temperature by means of gas microphone

(scanning photoacoustic microscopy, SPAM), by measuring the

deflection of a laser beam transversing through a liquid or gas layer

adjacent to the heated surface (optical beam deflection) or by

detecting the infra-red radiation emitted from the sample surface. The

spatial resolution is determined by the spot size of the incident beam,

the thermal wavelength, and thermal conductivity ranging for metals

[i.e. thermal conductors] from a few µm at high modulation frequency

(1MHz) to a few mm at 100Hz. For thermal insulators, resolution is

approximately one order of magnitude better. Since the depth of

penetration into the material is proportional to the wavelength, the

bulk of a sample can be reached at low frequencies, and

thermoacoustic signals can be detected by ultrasonic transducers

attached to the sample. This technique allows three-dimensional

information to be obtained simply by changing the frequency and has

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been termed thermoacoustic probe. Usually, thermal wave imaging

systems are attached to scanning electron microscopes using

excitation by the electron beam.

Applications of both the thermal-wave microscope and the

thermoacoustic probe have been mostly restricted to the investigation

of microelectronic components where most of the features of interest

lie within 10 µm of the surface. However, owing to the fact that the

thermal waves are more sensitive to local variations in lattice structure

than photons (optical or x-ray) and have a better resolution than

acoustic and x-ray imaging, there are numerous potential applications

for other materials, e.g. for detection of planes and grains in alloys or

composites without special contrasting or in-situ investigation during

dynamic studies.

5.3 FIELD – ELECTRON AND FIELD – ION EMISSION

Very high gradients of electric fields at the surface of a metal cause emission

of electrons and ions. This is the basis of field-electron and field-ion

microscopy.

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5.3.1 FIELD – ELECTRON MICROSCOPY

Field-electron microscopes (FEMs) are non-commercially made laboratory

equipment in which an etched single-crystal tip is heated in high vacuum.

The emitted electrons are accelerated by an anode and produce an image on

a fluorescent screen. The intensity of electrons emitted (field emission

current) depends on the voltage and the work of emission; the lattice

structure and local geometric structure of surfaces can be studied with high

resolution down to a few nanometers.

The crystallographic structure of clean surfaces and (if by chance a grain

boundary was located in the tip) the structure and the movement of grain

boundaries as well as changes of the tip material during heating have been

studied; by measuring the energy distribution of the field electrons the

electronic structure of the single-crystal tip can be investigated. Adsorption

of gas from the vacuum chamber or of evaporated substances (metal or

oxides) changes the image drastically, which has been used for studying the

sites of adsorption, the migration of adsorbed species along grain boundaries

and the formation of compounds.

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5.3.2 FIELD-ION EMISSION AND FIELD-ION DESORPTION

MICROSCOPY AND THE ATOM PROBE

Compared with field-electron microscopy, much higher resolutions, down to

atomic dimensions (< 0.15 nm), are achieved in field ion microscopy (FIM).

Noble gas atoms (usually Helium) are ionized at the cooled surface of a

pointed metal tip. The ions are accelerated by a high voltage and hit a

channel plate converter which produces and multiplies secondary electrons

which are emitted radially to a fluorescent screen. In this way, a high

resolution image of the tip is obtained showing individual atoms and their

arrangement.

Terrace steps ionize most strongly and, therefore, appear bright. Lattice

defects cut by the tip surface, such as dislocations, stacking faults, grain

boundaries and anti-phase boundaries in ordered structures are revealed.

Vacancies and interstitials can be observed and their movement studied by

taking photographs after certain time intervals. Moiré simulation can be used

to provide a simple and direct means of visualizing the physical

interpretation of field-ion micrographs.9, 11

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If the field –ion microscope is combined with a time-of-flight (TOF) mass

spectrometer, the chemical nature of atoms pulled off the tip surface by a

very large high voltage impulse can be identified. The atom passes a hole in

the screen and hits a detector, and from TOF the specific mass is calculated.

By positioning the tip with respect to the aperture hole, it is possible to focus

each individual atom (FIM atom-probe). The same physical principle allows

to analyze the chemical composition of the entire tip in the field desorption

microscope (FDS). The image is formed by the desorbed atoms by activating

the screen with a pulsed potential. Successive layers of the tip can be

analyzed in this way (field evaporation). Using this technique the

morphology, crystallography and chemistry of special alloys and particles in

statunascends can be analyzed.

Furthermore, in-situ studies of radiation damage, adsorption and desorption,

nucleation and all other investigations mentioned above for field-electron

microscopy can be carried out by field-ion microscopy and the atom probe.

5.4 PHOTON - INDUCED RADIATION

A variety of kinds of radiation can be produced by photons hitting the

surface of a material. X-ray diffraction, which shall not be considered in this

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work, is used most widely in the study of metals. Here, a short account is

given of two other methods capable of producing surface images.

5.4.1 X-RAY MICROSCOPY AND TOPOGRAPHY

Soft x-ray microscopy was developed early but was then overshadowed by

the rapid growth of electron microscopy. More recently, with synchrotron

radiation available, high resolution scanning x-ray microscopy has proved to

possess positive features (high contrast especially) in materials

investigations.

For studying defects in the surface of single crystals, x-ray topography is a

useful technique. The penetration depth of 5µm and a lateral resolution of

>1µm restricts application to relatively perfect crystals (defect density <

105/cm2) but owing to its high selectivity for different types of defects and

their location (sub-grain boundaries, stacking faults, structure of

ferromagnetic domains, dislocations) x-ray topography has become a

standard technique for monitoring crystal quality, especially in the

semiconductor industry. A classical study is the investigation of the internal

magnetic structure of non-transparent ferromagnetic crystals. It is not

possible to magnify the image directly, owing to the lack of x-ray lenses.

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High-resolution film and photographic magnification has been widely used,

typical exposure times ranging from 10 min. to 2 hours with a 1kW x-ray

source. More recently, digital image storage and accumulation have become

available, providing better resolution and higher speed.

5.4.2 FLOURESCENCE MICROSCOPY AND SPECTROSCOPY

If a fluorescing substance is irradiated by photons (x-rays or light of short

wavelength, usually ultraviolet), some of the energy is re-emitted as light of

longer wavelength which is typical for the substance. This effect is called

fluorescence and is used in mineralogy for identification purposes and, in

biology after suitable staining with fluorescent substances. Very few phases

in metallic alloys are fluorescent; therefore this technique is rarely used.

Extremely small amounts of fluorescent nonmetallic phases can be detected

in this way.

For chemical analysis, x-ray fluorescence has been widely used in the last

five decades and has become a standard technique in materials science and

technology. The average composition of large areas (approximately 10cm2)

and relatively thick surface layers (about 100µm) is obtained by analyzing

the x-ray spectra excited by a high-intensity x-ray beam which has a wide

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wavelength distribution in order to assess all elements in a wide range of

atomic numbers (9- 92). Concentrations from some ppm to 100% can be

evaluated with a relative accuracy up to 0.2%.

5.5 PHOTO-ELECTRON EMISSION

Electrons excited by photons are used for high-resolution imaging and for

chemical analysis of surface and thin films.

5.5.1 PHOTO-ELECTRON EMISSION MICROSCOPY

In photo-electron emission microscopes (PEEM), a high-intensity beam of

UV light is focused by means of quartz lenses and mirrors on a small area of

surface which activates emission of relatively slow electrons. The instrument

has been applied for studies in materials research, providing much

interesting information in all kinds of high-quality metallographic work.

Owing to the very small depth of information (10nm), the excellent phase

separation and the possibility for in-situ heating, photo-electron microscopy

is excellently capable for quantitative kinetic studies of changes in

microstructural geometry. It has been used to reveal the bonding sequence

(grain-boundary movement and annihilation) during diffusion-bonding of

steel under load of temperatures up to 10000C.

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5.5.2 PHOTO-ELECTRON SPECTROSCOPY

The kinetic energy of photo-electrons leaving the surface can be analyzed by

a spectrometer. From the electrum energy spectrum, the chemical

composition is obtained by calculating the binding energy of the emitted

electrons. This technique is usually called ESCA (i.e. electron spectroscopy

for chemical analysis); more precisely, XPS (x-ray-induced photoelectron

spectroscopy) and UPS (ultraviolet light-excited photoelectron

spectroscopy) are differentiated.

Typical applications of ESCA are the exact characterization of oxide layers

formed on metal surfaces (allowing not only to specify composition of the

oxidation products but also the electronic state of the metal atoms in the

oxides), and investigations of catalytic reactions (chemical changes of

catalysts as well as of adsorbed species).

5.6 ELCTRON-BEAM AND ION-INDUCED RADIATION

X-rays are excited when an electron-beam hits a surface. Also, an incident

beam used for surface microscopy can also create electron-hole pairs.

During recombination of these pairs, some materials emit long-wave

radiation known as cathodoluminescence (CL) which can be exploited in the

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SEM using suitable accessories. Biological and mineralogical applications

abound. These phenomena are exploited in (i) x-ray mapping, (ii) Energy –

dispersive x-ray spectroscopy (EDS), (iii) wavelength-dispersive x-ray

spectroscopy (WDS), cathodoluminescence mapping; as discussed in

sections 3.2.4 and 3.2.5 of this term paper.

Similarly as in x-ray fluorescence and electron beam-induced x-ray

spectroscopy, x-rays activated by charged particles (ions, mostly protons)

can be registered and analyzed with respect to intensity as a function of

energy. Particle-induced x-ray emission (PIXE) or ion-induced x-ray

emission (IIXE) was first introduced in nuclear physics where ion-

accelerating facilities were available; now this method has spread since

small accelerators are not much more expensive than other instruments

described so far. By using these techniques, fast chemical analysis of

elements with atomic numbers higher than 14 can be achieved with very

high sensitivity. The main fields of application have been in air pollution

and in biology; however, several interesting studies including the detection

of impurity traces in oxide layers, implantation and oxidation mechanisms of

steel have been reported.9

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5.7 ELECTRON-ELECTRON INTERACTION

Electron-beam-induced secondary electrons, Auger electrons and

backscattered electrons are most successfully used for surface imaging in the

SEM. In Auger-electron spectroscopy (AES), an electron detector and an

electron spectrometer are used to register the number of electrons N(E) as a

function of energy E and the differentiated signal dN(E)/dE is plotted and

analyzed. In scanning Auger Microscopy (SAM), the electron beam is

scanned, an image can be formed by activating a CRT modulated by the

signal intensity of the Auger electrons in the same way as in x-ray mapping.

AES and SAM techniques have been applied in a variety of problems

including studies of contamination, inhomogeneity, diffusion, and profile

analysis of thin layers, segregation in grain boundaries and oxide layers and

many other topics of scientific and technological importance.

Electron diffraction is another outcome of electron-electron interaction.

Electron diffraction methods investigate the stray angle distribution of a

monochromatic electron-beam scattered back from surface atoms. Low-

energy electron diffraction (LEED) uses primary energies between 10 and

500eV (corresponding to wavelengths of 0.4 – 0.05nm) and yields

information on the structure and electronic bonding states of surface atoms.

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Reflection high-energy electron diffraction (RHEED) can be applied

similarly to x-ray diffraction, and is more sensitive to contamination and

deformation of the surface. Electron diffraction is advantageously used in

combination with other techniques of surface analysis, adding information

which cannot be obtained otherwise.

5.8 ION SPECTROSCOPY

Ions can leave the surface owing to excitation by photons, electrons, or ions,

or by scattering. The extremely high sensitivity of ion detectors can be used

for analyzing the chemical composition of surfaces down to minute scale.

Ion-scattering spectroscopy (ISS) also called ion-reflection spectroscopy and

Rutherford backscattering (RSS) is in competition with AES, and it seems it

is superseded at present in metallurgical applications.

Secondary-ion mass spectroscopy (SIMS) and its subcategories, ion-

microprobe mass analysis (IMMA) and statistical and dynamic secondary-

ion mass spectroscopy (SSIMS and DSIMS), rate among the most powerful

analytical instruments, revealing qualitative data on chemical traces in

surfaces with a sensitivity of better than 1ppm or 10-15g. SIMS and IMMA

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have been utilized to a large extent in the fields of mineralogy and

semiconductor technology but a number of applications in physical

metallurgy have been reported as well.9

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CHAPTER SIX

6.0 CONCLUSION

Materials scientists and engineers, metallurgists, physical chemists, solid-

state physicist, and geophysical scientists all owe a lot of thanks to Henry

Sorby for opening up a new world to the microscopist. In the second half of

the nineteenth century (and particularly in 1886) he looked at metals as

never before and revealed grains and structures by employing ‘higher

powers’. Utilizing reflected light techniques the microscope was to be an

industrial tool as industry required materials to function in many different

ways; the microscope was the key – the fingerprint of metallography. It is

now more than just a research tool; it is used for quality control of

components to ensure there are no weak links in the chain of manufacture of

articles.5, 15

Every item we touch or see has at some time been investigated by

microscopist: nearly every object has a microstructure and this is what the

microscopist is looking for. The condition of this structure tells us all: why

the bolt failed, why the bridge collapsed, why the paint peeled off, etc.

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Microscopy has become a vital science in the quality control of materials

and components, without which our confidence in traveling on airplanes, in

motor cars, on trains, etc. would be greatly reduced. New engineering

materials have brought a new dimension in our microscopic studies since we

are required not just to observe the material grain structure but also the

relationship of one composite with another. There is therefore a great

demand upon the materials technologist to make the maximum use of all

microscopic techniques and exploit all applications of microscopy (optical

and electron-optical) in materials science and engineering.

Thank God that modern technological development in electronics and

computers have improved the speed and quality of results obtained in

microscopy. University and industrial laboratories now routinely undertake

types of analysis that would formerly have required the effort for a PhD

thesis.

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REFERENCES

1. ASM Metals Handbook, vol. 9, 1985: Metallography and

Microstructures. American Society for Metals, Metals Park,

Ohio.

2. ASM Metals Handbook, vol. 10, 1986: Materials Characterization.

American Society for Metals, Metals Park, Ohio.

3. Barret, C. & Massalki, T. B. 1992: Structure of Metals –

Crystallographic Methods, Principles, and Data. 3rd Revised

Edition. Pergamon Press, England. pp. 418 – 419, 430.

4. Bethge, H. & Heydenreich, J (eds.), 1987. Electron Microscopy in

Solid – State Physics. VEB Deutscher, Berlin. pp. 287 – 526.

5. Bousfield, Brian. 1992: Surface Preparation and Microscopy of

Materials. (For Buchler Europe Ltd, Coventry, UK). John

Willey & Sons, England. pp. 1-3, 229-230

6. Buseck, P; Cowley, J & Eyring, L. (eds). 1988: High-Resolution

Transmission Electron Microscopy and Associated

Techniques. Oxford Uni. Press, NY. pp v-vii (preface).

7. Colliex, C & Mory, C. 1984: Quantitative Aspects of Scanning

Transmission Electron Microscopy, in Chapman, J. N and

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Craven, A.J (eds.): Proceedings of the Twenty-fifth Scottish

Universities Summer School in Physics, Glassgow, August

(1983). A NATO Advanced Study Institute. Redwood Burn

Ltd, UK. pp. 149-150.

8. Cottrell, A. H. 1975: An Introduction to Metallurgy, Second

Edition, Edward Arnold (publishers), London. pp. 1-8

9. Exner, H. E. 1983: Qualitative and Quantitative Surface

Microscopy. Chapter 10A of Physical Metallurgy – Third,

revised and enlarged edition, Part 1, 1992 Reprint. Cahn, R.W

& Haseen, P (eds.), Elsevier Sc. Pub. B.V. pp. 581-637.

10. Feder, R, McGowan, R. Wm & Shinozaki, D.M (eds.), 1986:

Examining the Submicron World – A NATO Advanced

Science Institute Series. Plenum Press, NY. pp. preface,

133 – 136

11. Geller, A. Yu & Rakhshtadt, A. G. 1977: Science of Materials;

Methods of Analysis, Laboratory Exercises and Problems.

(Translated from the Russian by V. Afanasyev). Mir Publishers,

Moscow. pp. 15 – 103.

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12. Grundy, P. J. & Jones, G. A. 1976: Electron Microscopy in the

Study of Materials. (The Structures and properties of Solids

Series 7), Edward Arnold, London.

13. Guy, A. G. 1976: Essentials of Materials Science. McGraw – Hill,

Tokyo. pp. 34 – 48, 57.

14. Lifshin, E. 1986: Investigation and Characterization of Materials.

In Bever, M. B (ed), Encyclopedia of Materials Science and

Engineering, vol.3, Pergamon Press / The MIT press.

pp. 2389 – 2398.

15. Raghavan, V. 1990: Materials Science and Engineering – A First

Course, third edition. Prentice – Hall of India, New Delhi.

pp. 1-7

16. Rajput, R. K. 2004: Engineering Materials, 2nd edition. S. Chand,

India. p.407.

17. Reed-Hill, R. E & Abbaschian, R. 1992: Physical Metallurgy

Principles – Third Edition. PWS – KENT pub. Co., Boston.

pp. 33 – 67.

18. Smith, W. F. 1990: Materials Science and Engineering. McGraw-

Hill, NY. pp. 1 – 13.

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